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JP6713106B2 - Lead-free solder alloy, solder material and joint structure - Google Patents

Lead-free solder alloy, solder material and joint structure Download PDF

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Publication number
JP6713106B2
JP6713106B2 JP2016504153A JP2016504153A JP6713106B2 JP 6713106 B2 JP6713106 B2 JP 6713106B2 JP 2016504153 A JP2016504153 A JP 2016504153A JP 2016504153 A JP2016504153 A JP 2016504153A JP 6713106 B2 JP6713106 B2 JP 6713106B2
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mass
solder alloy
solder
lead
less
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JPWO2015125855A1 (en
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淳 入澤
淳 入澤
理枝 和田
理枝 和田
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Koki Co Ltd
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Koki Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/262—Sn as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin
    • C22C13/02—Alloys based on tin with antimony or bismuth as the next major constituent
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    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
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  • Materials Engineering (AREA)
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  • Organic Chemistry (AREA)
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  • Electric Connection Of Electric Components To Printed Circuits (AREA)

Description

関連出願の相互参照Cross-reference of related applications

本願は、日本国特願２０１４−３３２３４号の優先権を主張し、引用によって本願明細書の記載に組み込まれる。 This application claims the priority of Japanese Patent Application No. 2014-33234, and is incorporated into the description of the present specification by reference.

本発明は、電子部品のはんだ付けに用いられる鉛フリーはんだ合金、これを含むはんだ材料及び前記鉛フリーはんだ合金を含む接合構造体に関する。 The present invention relates to a lead-free solder alloy used for soldering an electronic component, a solder material containing the same, and a joint structure containing the lead-free solder alloy.

近年、環境問題の観点から鉛をほとんど含まない鉛フリーはんだが、プリント配線板等の電子回路基板に電子部品を実装するために用いられている。
一方、実装基板及び配線の微細化に伴い、部品の微小化も進み、その結果、はんだ接合部の微小化も進んでいる。In recent years, lead-free solder containing almost no lead has been used for mounting electronic components on electronic circuit boards such as printed wiring boards from the viewpoint of environmental problems.
On the other hand, with the miniaturization of the mounting board and wiring, the miniaturization of components is also progressing, and as a result, the miniaturization of solder joints is also progressing.

かかるはんだ接合部の微小化に伴い、エレクトロマイグレーション（electromigration）の発生によるはんだ接合部におけるボイド、さらには、断線が問題になってきている。そこで、鉛フリーはんだにおいてエレクトロマイグレーションを抑制するための技術が種々検討されている。 With the miniaturization of such solder joints, voids in the solder joints due to occurrence of electromigration and further disconnection have become a problem. Therefore, various techniques for suppressing electromigration in lead-free solder have been studied.

例えば、特許文献１には、接続端子表面にＡｇ−Ｓｎ金属からなる保護層を設けることが記載されている。しかし、このように接続端子表面に保護層を設ける場合には、接続構造そのものを変更する必要が生じ、大幅に製造工程の見直しが必要になる。また、保護層を設ける工程が必要になり、製造工程が煩雑になる。そこで、はんだ合金の組成を調整することで、エレクトロマイグレーションを抑制することが検討されている。例えば、特許文献２には、Ｃｕ及びＩｎを特定の含有量含み残部がＳｎである鉛フリーはんだ合金が記載されている。また、特許文献３には、Ｐｄ、Ｍｎ、Ｚｎ、Ａｌ、Ｓｂ、Ｉｎ等の金属を含む鉛フリーはんだ合金が記載されている。
しかし、特許文献２及び３に記載のはんだ合金では、エレクトロマイグレーションを抑制する効果が不十分である。For example, Patent Document 1 describes that a protective layer made of Ag—Sn metal is provided on the surface of the connection terminal. However, when the protective layer is provided on the surface of the connection terminal as described above, it is necessary to change the connection structure itself, and the manufacturing process needs to be significantly revised. In addition, the step of providing the protective layer is required, which complicates the manufacturing process. Therefore, it has been considered to suppress electromigration by adjusting the composition of the solder alloy. For example, Patent Document 2 describes a lead-free solder alloy in which Cu and In are contained in specific contents and the balance is Sn. Further, Patent Document 3 describes a lead-free solder alloy containing a metal such as Pd, Mn, Zn, Al, Sb, and In.
However, the solder alloys described in Patent Documents 2 and 3 are insufficient in the effect of suppressing electromigration.

日本国特開２０１３−１３５０１４号Japanese Patent Laid-Open No. 2013-135014 日本国特開２０１３−２５２５４８号Japanese Patent Laid-Open No. 2013-252548 日本国特開２０１４−２７１２２号Japanese Unexamined Patent Publication No. 2014-27122

本発明は、前記のような従来技術の問題点に鑑みてなされたものであり、はんだ接合部におけるエレクトロマイグレーションの発生を十分に抑制しうる鉛フリーはんだ合金、はんだ材料及び接合構造体を提供することを課題とする。 The present invention has been made in view of the above-mentioned problems of the prior art, and provides a lead-free solder alloy, a solder material, and a bonding structure capable of sufficiently suppressing the occurrence of electromigration in a solder bonding portion. This is an issue.

本発明の鉛フリーはんだ合金は、Ｓｂを３．０質量％超１０質量％以下含み、残部としてＳｎを含む。 The lead-free solder alloy of the present invention contains more than 3.0% by mass and 10% by mass or less of Sb, and Sn as the balance.

本発明の鉛フリーはんだ合金は、残部としてさらにＡｇ、Ｃｕ、Ｎｉ、Ｃｏ及びＧｅからなる群から選択される少なくとも一種の金属を含んでいてもよい。 The lead-free solder alloy of the present invention may further contain at least one metal selected from the group consisting of Ag, Cu, Ni, Co and Ge as the balance.

本発明の鉛フリーはんだ合金は、前記Ａｇを４．０質量％以下含んでいてもよい。 The lead-free solder alloy of the present invention may contain the Ag in an amount of 4.0 mass% or less.

本発明の鉛フリーはんだ合金は、前記Ｃｕを１．０質量％以下含んでいてもよい。 The lead-free solder alloy of the present invention may contain 1.0% by mass or less of the Cu.

本発明の鉛フリーはんだ合金は、前記Ｎｉ、Ｃｏ及びＧｅを合計で０．１質量％以下含んでいてもよい。 The lead-free solder alloy of the present invention may contain 0.1% by mass or less of Ni, Co and Ge in total.

本発明のはんだ材料は、前記鉛フリーはんだ合金と、フラックスとを含む。 The solder material of the present invention contains the lead-free solder alloy and a flux.

本発明の接合構造体は、電極を有する基板と半導体素子とがはんだ接合部を介して接合された接合構造体であって、前記はんだ接合部は、前記鉛フリーはんだ合金を含む。 The joint structure of the present invention is a joint structure in which a substrate having an electrode and a semiconductor element are joined via a solder joint, and the solder joint includes the lead-free solder alloy.

テストピースの概略を示すＳＥＭ写真。The SEM photograph which shows the outline of a test piece. エレクトロマイグレーション試験に用いた装置の概要を示す該略図。The schematic diagram showing the outline of the apparatus used for the electromigration test.

以下に、本発明に係る鉛フリーはんだ合金、はんだ材料及び接合構造体について説明する。 The lead-free solder alloy, the solder material, and the joint structure according to the present invention will be described below.

まず、本実施形態の鉛フリーはんだ合金は、Ｓｂ（アンチモン）を３．０質量％超１０質量％以下含み、残部がＳｎ（錫）である鉛フリーはんだ合金である。
尚、本実施形態において残部とはＳｂ以外の成分を意味する。First, the lead-free solder alloy of the present embodiment is a lead-free solder alloy that contains more than 3.0% by mass and 10% by mass or less of Sb (antimony) and the balance is Sn (tin).
In the present embodiment, the balance means a component other than Sb.

本実施形態の鉛フリーはんだ合金は、ＪＩＳ Ｚ ３２８２に定める鉛フリーはんだに用いられるはんだ合金をいう。 The lead-free solder alloy of this embodiment is a solder alloy used for lead-free solder defined in JIS Z3282.

本実施形態の鉛フリーはんだ合金（以下、単にはんだ合金ともいう。）は、Ｓｂを３．０質量％超１０質量％以下、好ましくは３．３質量％以上５質量％以下含む。
本実施形態のはんだ合金はＳｎを主成分とする鉛フリーはんだ合金である。
かかるＳｎを主成分とするはんだ合金において、Ｓｂを前記範囲含むことにより、はんだ合金をはんだ接合に用いた場合に、エレクトロマイグレーションを十分に抑制することができる。
尚、本実施形態において、３．０質量％超とは、３．０質量％よりも大きい質量％を意味する。以下、「超」は同様の意味で用いられる。The lead-free solder alloy (hereinafter, also simply referred to as a solder alloy) of the present embodiment contains Sb in excess of 3.0% by mass and 10% by mass or less, preferably 3.3% by mass or more and 5% by mass or less.
The solder alloy of this embodiment is a lead-free solder alloy containing Sn as a main component.
By including Sb in the above range in the solder alloy containing Sn as a main component, electromigration can be sufficiently suppressed when the solder alloy is used for solder joining.
In addition, in this embodiment, more than 3.0 mass% means mass% larger than 3.0 mass %. Hereinafter, “super” is used with the same meaning.

エレクトロマイグレーションは、金属中に高密度電流が流れた際に、金属電子が移動する現象であり、かかる、金属電子の移動によって金属部分に欠落部分（ボイド）が生じることになる。特に、実装部品の微細化によってはんだ接合部が微小になると、電流が少なくても電流密度が高くなるため、エレクトロマイグレーションが発生しやすくなる。例えば、半導体素子とインターポーザー基板とを電気的に接続するインナーバンプのようなはんだ接合部等のように、従来のプリント基板の部品実装におけるはんだ接合部に比べて極めて微小なはんだ接合部においては、はんだ接合部に高密度電流が流れてエレクトロマイグレーションが発生し、ボイド、あるいは、断線等が生じる虞がある。かかるエレクトロマイグレーションは、通常、１０ｋＡ／ｃｍ２以上のような高密度電流で発生しやすくなるが、はんだ接合部が球状のバンプである場合には、バンプ径が８０μｍのバンプの場合には３１．４ｍＡ程度の電流でも電流集中部において１０ｋＡ／ｃｍ２以上の高密度電流が流れる可能性がある。よって、はんだ接合部が小さくなるほどより小さい電流でもエレクトロマイグレーションが発生しやすくなる。Electromigration is a phenomenon in which metal electrons move when a high-density current flows in the metal, and the movement of the metal electrons causes a missing portion (void) in the metal portion. In particular, if the solder joints become minute due to the miniaturization of mounted components, the current density becomes high even if the current is small, so that electromigration easily occurs. For example, in solder joints such as inner bumps that electrically connect a semiconductor element and an interposer substrate, extremely small solder joints as compared with solder joints in conventional component mounting of printed circuit boards. A high-density current may flow in the solder joint to cause electromigration, resulting in voids or disconnection. Such electromigration usually tends to occur at a high-density current such as 10 kA/cm 2 or more, but when the solder joint is a spherical bump, 31. When the bump diameter is 80 μm. Even with a current of about 4 mA, a high-density current of 10 kA/cm 2 or more may flow in the current concentrating portion. Therefore, as the solder joint becomes smaller, electromigration easily occurs even with a smaller current.

本実施形態のはんだ合金は、エレクトロマイグレーションが発生しにくいため、特に、半導体素子とインターポーザー基板とを電気的に接続するインナーバンプのような微小はんだ接合部に好適に用いられる。 Since the solder alloy of the present embodiment is unlikely to cause electromigration, it is particularly suitable for use in minute solder joints such as inner bumps that electrically connect a semiconductor element and an interposer substrate.

本実施形態のはんだ合金は、例えば、溶融開始温度である固相線温度が２２０℃〜２４０℃、好ましくは２３０℃〜２３６℃、凝固開始温度である液相線温度が２２１℃〜２５０℃、好ましくは２３０℃〜２４５℃の範囲である。
前記範囲の固相線温度及び液相線温度であることで、エレクトロマイグレーションを抑制しつつ、はんだ合金の流動性を適切な範囲に維持でき、且つはんだ接合後の溶融を抑制することができる。The solder alloy of the present embodiment has, for example, a solidus temperature that is a melting start temperature of 220° C. to 240° C., preferably 230° C. to 236° C., and a liquidus temperature that is a solidification start temperature of 221° C. to 250° C. It is preferably in the range of 230°C to 245°C.
When the solidus temperature and the liquidus temperature are within the above ranges, the fluidity of the solder alloy can be maintained in an appropriate range while suppressing electromigration, and melting after soldering can be suppressed.

一般的にＳｎを主成分とする鉛フリーはんだ合金は、Ｓｎよりも溶融温度の低い鉛を含まないため、溶融温度が高いことが知られている。そこでＳｎよりも溶融温度の低い金属を含む合金とすることではんだ合金の溶融温度を調整することができる。一方、溶融温度が低くなりすぎると、例えば、前述のようなインナーバンプに用いられた場合に、マザーボードとなる基板に部品を実装する際に、インナーバンプが溶融してしまうという問題が起きる。よって、インナーバンプに用いられるはんだ合金は液相線温度が例えば、汎用鉛フリーはんだ（Ｓｎ３Ａｇ０．５Ｃｕ）の液相線温度である２２０℃以上であることが好ましい。
本実施形態のはんだ合金は溶融温度が前記範囲であることで、エレクトロマイグレーションを抑制しつつ、はんだ合金の流動性を適切な範囲に維持でき、且つはんだ接合後の溶融を抑制することができる。It is known that a lead-free solder alloy containing Sn as a main component generally has a high melting temperature because it does not contain lead having a lower melting temperature than Sn. Therefore, the melting temperature of the solder alloy can be adjusted by using an alloy containing a metal having a lower melting temperature than Sn. On the other hand, if the melting temperature becomes too low, for example, when used for the inner bump as described above, the inner bump melts when the component is mounted on the substrate to be the motherboard. Therefore, it is preferable that the liquidus temperature of the solder alloy used for the inner bump is, for example, 220° C. or higher which is the liquidus temperature of general-purpose lead-free solder (Sn3Ag0.5Cu).
When the melting temperature of the solder alloy of the present embodiment is within the above range, the fluidity of the solder alloy can be maintained in an appropriate range while suppressing electromigration, and melting after solder joining can be suppressed.

本実施形態のはんだ合金は、残部としてＳｎ以外に、Ａｇ（銀）、Ｃｕ（銅）、Ｎｉ（ニッケル）、Ｃｏ（コバルト）及びＧｅ（ゲルマニウム）からなる群から選択される少なくとも一種の金属をさらに含んでいてもよい。
これらの金属をさらに含むことで、よりエレクトロマイグレーションを抑制できる。In addition to Sn, the solder alloy of the present embodiment contains at least one metal selected from the group consisting of Ag (silver), Cu (copper), Ni (nickel), Co (cobalt), and Ge (germanium) as the balance. It may further include.
By further containing these metals, electromigration can be further suppressed.

残部中の各金属の好ましい含有量は、特に限定されるものではないが、たとえば、Ｓｎは９４．９質量％以上１００質量％以下、好ましくは、９６質量％以上１００質量％以下である。
また、Ａｇ、Ｃｕ、Ｎｉ、Ｃｏ及びＧｅの総量は、残部のうちの０．００１質量％以上５．１質量％以下、好ましくは、０．５質量％以上４．０質量％以下である。The preferred content of each metal in the balance is not particularly limited, but for example, Sn is 94.9% by mass or more and 100% by mass or less, preferably 96% by mass or more and 100% by mass or less.
The total amount of Ag, Cu, Ni, Co and Ge is 0.001 mass% or more and 5.1 mass% or less of the balance, and preferably 0.5 mass% or more and 4.0 mass% or less.

各成分のより具体的な含有量は、例えば、以下のとおりである。
本実施形態のはんだ合金は、Ｓｎを８４．４質量％以上９７．０質量％以下含んでいてもよい。
本実施形態のはんだ合金は、Ａｇを０．１質量％以上４．５質量％以下、好ましくは１．０質量％以上３．５質量％以下含んでいてもよい。
Ａｇを前記範囲含むことで、よりエレクトロマイグレーションを抑制できる。More specific contents of each component are as follows, for example.
The solder alloy of the present embodiment may contain Sn in an amount of 84.4% by mass or more and 97.0% by mass or less.
The solder alloy of the present embodiment may contain Ag in an amount of 0.1% by mass or more and 4.5% by mass or less, preferably 1.0% by mass or more and 3.5% by mass or less.
By including Ag in the above range, electromigration can be further suppressed.

本実施形態のはんだ合金が、Ｃｕを含む場合には、０．１質量％以上１．２質量％以下、好ましくは０．５質量％以上０．７質量％以下含んでいてもよい。
本実施形態のはんだ合金が、Ｎｉを含む場合には、０．０１質量％以上０．１質量％以下、好ましくは０．０３質量％以上０．０７質量％以下含んでいてもよい。
本実施形態のはんだ合金は、Ｃｏを含む場合には、０．０１質量％以上０．１質量％以下、好ましくは０．０３質量％以上０．０７質量％以下含んでいてもよい。
本実施形態のはんだ合金は、Ｇｅを含む場合には、０．００１質量％以上０．１質量％以下、好ましくは０．００５質量％以上０．０１質量％以下含んでいてもよい。
尚、Ｎｉ、Ｃｏ、Ｇｅの合計の含有量としては、０質量％超０．１質量％以下であってもよい。
この場合、Ｎｉ、Ｃｏ、Ｇｅの合計の含有量とは、Ｎｉ、Ｃｏ及びＧｅからなる群から選択される少なくとも一種の金属の合計量を意味し、一種のみの場合にはその金属の含有量を意味する。
Ｃｕ、Ｎｉ、Ｃｏ、Ｇｅを前記範囲含むことで、よりエレクトロマイグレーションを抑制できる。When the solder alloy of the present embodiment contains Cu, it may be contained in an amount of 0.1% by mass or more and 1.2% by mass or less, preferably 0.5% by mass or more and 0.7% by mass or less.
When the solder alloy of the present embodiment contains Ni, it may be contained in an amount of 0.01% by mass or more and 0.1% by mass or less, preferably 0.03% by mass or more and 0.07% by mass or less.
When the solder alloy of the present embodiment contains Co, it may contain 0.01 mass% or more and 0.1 mass% or less, preferably 0.03 mass% or more and 0.07 mass% or less.
In the case where Ge contains Ge, the solder alloy of the present embodiment may contain 0.001% by mass or more and 0.1% by mass or less, preferably 0.005% by mass or more and 0.01% by mass or less.
The total content of Ni, Co, and Ge may be more than 0 mass% and 0.1 mass% or less.
In this case, the total content of Ni, Co and Ge means the total content of at least one metal selected from the group consisting of Ni, Co and Ge, and in the case of only one, the content of the metal. Means
By including Cu, Ni, Co, and Ge in the above range, electromigration can be further suppressed.

すなわち、本実施形態のはんだ合金の一例としては、Ｓｂを３．０質量％超１０質量％以下と、残部としてのＳｎとからなる鉛フリーはんだ合金が挙げられる。
この場合、残部はＳｎ１００質量％である。That is, as an example of the solder alloy of the present embodiment, there is a lead-free solder alloy containing Sb in excess of 3.0% by mass and 10% by mass or less, and the balance Sn.
In this case, the balance is 100 mass% Sn.

また、本実施形態のはんだ合金の他の一例としては、Ｓｂを３．０質量％超１０質量％以下含み、残部がＳｎと、Ａｇ、Ｃｕ、Ｎｉ、Ｃｏ及びＧｅからなる群から選択される少なくとも一種の金属とからなる鉛フリーはんだ合金が挙げられる。
この場合、残部は、Ｓｎが８４．６９質量％以上９６．９９９質量％以下、Ａｇ、Ｃｕ、Ｎｉ、Ｃｏ及びＧｅからなる群から選択される少なくとも一種の金属の合計量が３．００１質量％以上１５．３１質量％以下である。Further, as another example of the solder alloy of the present embodiment, Sb is contained in an amount of more than 3.0% by mass and 10% by mass or less, with the balance being Sn, and selected from the group consisting of Ag, Cu, Ni, Co and Ge. A lead-free solder alloy composed of at least one kind of metal can be used.
In this case, the balance of Sn is 84.69 mass% or more and 96.999 mass% or less, and the total amount of at least one metal selected from the group consisting of Ag, Cu, Ni, Co and Ge is 3.001 mass %. The above is 15.31% by mass or less.

尚、本実施形態のはんだ合金は、残部として不可避不純物を含んでいてもよい。
この場合には、本実施形態のはんだ合金の一例としては、Ｓｂを３．０質量％超１０質量％以下と、残部としてのＳｎ及び不可避不純物とからなる鉛フリーはんだ合金である。
また、本実施形態のはんだ合金の他の一例としては、Ｓｂを３．０質量％超１０質量％以下含み、残部がＳｎと、Ａｇ、Ｃｕ、Ｎｉ、Ｃｏ及びＧｅからなる群から選択される少なくとも一種の金属と不可避不純物とからなる鉛フリーはんだ合金である。The solder alloy of this embodiment may contain unavoidable impurities as the balance.
In this case, an example of the solder alloy of the present embodiment is a lead-free solder alloy containing Sb in excess of 3.0% by mass and 10% by mass or less, and the balance Sn and inevitable impurities.
Further, as another example of the solder alloy of the present embodiment, Sb is contained in an amount of more than 3.0% by mass and 10% by mass or less, with the balance being Sn, and selected from the group consisting of Ag, Cu, Ni, Co and Ge. It is a lead-free solder alloy composed of at least one metal and unavoidable impurities.

尚、本実施形態において前記各金属の含有量は、スパーク放電発光分光分析を用いて、ＪＩＳ Ｚ ３９１０に記載の方法によって測定した値をいう。 In addition, in this embodiment, the content of each metal means a value measured by a method described in JIS Z 3910 using spark discharge optical emission spectroscopy.

次に、前述のような本実施形態のはんだ合金を用いたはんだ材料について説明する。
本実施形態のはんだ材料は、前記鉛フリーはんだ合金と、フラックスとを含むはんだ材料である。Next, a solder material using the solder alloy of the present embodiment as described above will be described.
The solder material of the present embodiment is a solder material containing the lead-free solder alloy and flux.

フラックスは、特に限定されるものでなく、公知のフラックスを用いることができるが、例えば、ロジン系、合成樹脂系等、公知のはんだ材料に用いられるものが挙げられる。 The flux is not particularly limited, and a known flux can be used, and examples thereof include those used for known solder materials such as rosin-based and synthetic resin-based fluxes.

本実施形態のはんだ材料における、はんだ合金及びフラックスの含有量は特に限定されるものではないが、例えば、はんだ合金８５質量％以上９５質量％以下、好ましくは８８質量％以上９０質量％以下、フラックス５質量％以上１５質量％以下、好ましくは１０質量％以上１２質量％以下である。 In the solder material of the present embodiment, the content of the solder alloy and the flux is not particularly limited, for example, the solder alloy 85 mass% or more 95 mass% or less, preferably 88 mass% 90 mass% or less, the flux It is 5% by mass or more and 15% by mass or less, preferably 10% by mass or more and 12% by mass or less.

本実施形態のはんだ材料に用いるはんだ合金は粉末状であることが好ましい。粉末状のはんだ合金である場合には、前記フラックスと混合することで、ペースト状のはんだ材料（ソルダーペースト）とすることが容易にできる。 The solder alloy used in the solder material of this embodiment is preferably in powder form. In the case of a powdered solder alloy, it can be easily made into a paste-like solder material (solder paste) by mixing with the flux.

尚、本実施形態のはんだ合金は、前述のように粉末状にしてフラックスと混合してソルダーペースト等として使用する以外にも、棒状、帯状、あるいは球状等の種々の形状に成形して使用してもよい。 The solder alloy of the present embodiment is used in the form of various shapes such as rod-shaped, band-shaped, or spherical, in addition to being used in the form of powder as described above and mixed with flux to be used as a solder paste or the like. May be.

次に、前述のような本実施形態のはんだ合金及びはんだ材料が用いられた接合構造体について説明する。
本実施形態のはんだ接合体は、電極を有する基板と半導体素子とがはんだ接合部を介して接合された接合構造体であって、前記はんだ接合部は、前述の本実施形態の鉛フリーはんだ合金を含んでいる。Next, a joint structure using the solder alloy and the solder material of the present embodiment as described above will be described.
The solder joint of the present embodiment is a joint structure in which a substrate having electrodes and a semiconductor element are joined via a solder joint, and the solder joint is the lead-free solder alloy of the present embodiment described above. Is included.

本実施形態の接合構造体は、電極を有する基板と半導体素子とがはんだ接合部を介して接合された接合構造体であって、前記はんだ接合部は、前述の鉛フリーはんだ合金を含む接合構造体である。 The bonding structure of the present embodiment is a bonding structure in which a substrate having an electrode and a semiconductor element are bonded via a solder bonding part, and the solder bonding part includes a bonding structure containing the lead-free solder alloy described above. It is the body.

電極を有する基板と半導体素子とがはんだ接合部を介して接合された接合構造体とは、例えば、フリップチップ実装によって形成された半導体パッケージが挙げられる。
フリップチップ実装によって形成された半導体パッケージは、半導体素子の下面にはんだバンプを形成し、基板上の電極とはんだ接合によって接続するもので、リード線を半導体素子の横に引き出す必要がなく、半導体素子のサイズに近い微小な半導体パッケージを得ることができる。
一方、かかる接合構造体におけるはんだ接合部は、極めて微小なサイズになるため、高密度電流が流れやすくエレクトロマイグレーションが発生しやすくなる。
さらに、かかる接合構造体のはんだ接合部は、接合構造体をさらにマザーボードとなる基板に実装する際にも熱にさらされることになるため、一度半導体素子を実装した後には容易に溶融しないことが要求される。Examples of the bonding structure in which the substrate having the electrodes and the semiconductor element are bonded via the solder bonding portion include a semiconductor package formed by flip chip mounting.
The semiconductor package formed by flip-chip mounting is one in which solder bumps are formed on the lower surface of the semiconductor element and connected to the electrodes on the substrate by solder bonding, and it is not necessary to pull out the lead wire to the side of the semiconductor element. It is possible to obtain a minute semiconductor package close to the size of
On the other hand, since the solder joint portion in such a joint structure has an extremely small size, a high-density current easily flows and electromigration easily occurs.
Further, since the solder joint portion of the joint structure is exposed to heat when the joint structure is further mounted on the substrate that will be the mother board, it may not be easily melted once the semiconductor element is mounted. Required.

本実施形態の接合構造体において、前述のような本実施形態のはんだ材料を用いた場合には、エレクトロマイグレーションを十分に抑制できると同時に、半導体素子を接合する際には適切な温度で溶融し、接合構造体を基板に実装する際には溶融することはない。 In the joint structure of the present embodiment, when the solder material of the present embodiment as described above is used, electromigration can be sufficiently suppressed and, at the same time, when the semiconductor element is joined, it melts at an appropriate temperature. When the bonding structure is mounted on the substrate, it does not melt.

尚、本実施形態のはんだ合金は、電極を有する基板と半導体素子とがはんだ接合部を介して接合された接合構造体のはんだ接合部に使用される以外にも、通常の電子部品とプリント基板の電極との接合部に用いてもよい。 The solder alloy of the present embodiment is used for a normal electronic component and a printed circuit board, in addition to being used for a solder joint portion of a joint structure in which a substrate having electrodes and a semiconductor element are joined via a solder joint portion. You may use it for the junction part with the electrode of.

本実施形態にかかるはんだ合金、はんだ材料および接合構造体は以上のとおりであるが、今回開示された実施の形態はすべての点で例示であって制限的なものではないと考えられるべきである。本発明の範囲は前記説明ではなくて特許請求の範囲によって示され、特許請求の範囲と均等の意味および範囲内でのすべての変更が含まれることが意図される。 Although the solder alloy, the solder material, and the bonding structure according to the present embodiment are as described above, the embodiments disclosed this time are to be considered as illustrative in all points and not restrictive. .. The scope of the present invention is shown not by the above description but by the scope of the claims, and is intended to include meanings equivalent to the scope of the claims and all modifications within the scope.

本発明の鉛フリーはんだ合金は、Ｓｂを３．０質量％超１０質量％以下含み、残部としてＳｎを含むため、接合部のはんだ材料として用いた場合にも、エレクトロマイグレーションを十分に抑制することができる。
よって、本発明によれば、はんだ接合部におけるエレクトロマイグレーションの発生を十分に抑制しうる鉛フリーはんだ合金、はんだ材料及び接合構造体を提供することができる。Since the lead-free solder alloy of the present invention contains more than 3.0% by mass and 10% by mass or less of Sb and Sn as the balance, it is possible to sufficiently suppress electromigration even when used as a solder material for a joint. You can
Therefore, according to the present invention, it is possible to provide a lead-free solder alloy, a solder material, and a joint structure capable of sufficiently suppressing the occurrence of electromigration in a solder joint.

次に、本発明の実施例について比較例と併せて説明する。なお、本発明は下記の実施例に限定して解釈されるものではない。 Next, examples of the present invention will be described together with comparative examples. The present invention should not be construed as being limited to the following examples.

（はんだ合金）
表１に記載の組成の各はんだ合金を準備した。(Solder alloy)
Each solder alloy having the composition shown in Table 1 was prepared.

Figure 0006713106
Figure 0006713106

（エレクトロマイグレーション耐性試験）
図１にエレクトロマイグレーション耐性を測定するためのテストピースの概略を示す。
テストピース（試験片）は、銅電極の間に、こて先２００μｍのはんだこて（ＵＮＩＸ−ＪＢＣ、ジャパンユニックス社製）を用いて各はんだ合金をはんだ付けすることで作製した。はんだ接合部の厚みは９μｍになるように調整した。
また、銅電極表面は＃２０００の耐水研磨紙を用いて研磨してから、＃４０００の耐水研磨紙を用いて仕上げ研磨した。
各テストピースを用いて、図２に示す装置でエレクトロマイグレーションを測定した。測定方法は、銅電極にプローブを接触させて、平均電流密度５０ｋＡ／ｃｍ２で通電して電圧値を測定した。テストピースは、セラミックヒータ上に載置して６０℃に加熱しながら通電した。
電圧値が測定不能になった時間を破断時間として表１に示す。
また、同様の測定方法で、実施例１，４及び比較例１について平均電流密度１００ｋＡ／ｃｍ２で、２００ｋＡ／ｃｍ２で通電して電圧値を測定し、電圧値が測定不能になった時間を破断時間として表２に示す。
さらに、実施例４及び比較例１については平均電流密度１０ｋＡ／ｃｍ２で通電して電圧値を測定し、電圧値が測定不能になった時間を破断時間として表２に示す。(Electromigration resistance test)
FIG. 1 shows an outline of a test piece for measuring electromigration resistance.
The test piece (test piece) was produced by soldering each solder alloy between the copper electrodes using a soldering iron having a tip of 200 μm (UNIX-JBC, manufactured by Japan Unix Co., Ltd.). The thickness of the solder joint was adjusted to be 9 μm.
The surface of the copper electrode was polished with #2000 water-resistant abrasive paper and then finish-polished with #4000 water-resistant abrasive paper.
Using each test piece, electromigration was measured by the device shown in FIG. As a measuring method, a probe was brought into contact with a copper electrode, and a voltage value was measured by energizing the probe with an average current density of 50 kA/cm 2 . The test piece was placed on a ceramic heater and energized while being heated to 60°C.
The time when the voltage value cannot be measured is shown in Table 1 as the breaking time.
Further, in the same measurement method, an average current density of 100 kA / cm 2 for Example 1, 4 and Comparative Example 1, to measure the voltage value and current at 200 kA / cm 2, the time in which the voltage value becomes unmeasurable Is shown in Table 2 as the breaking time.
Further, in Example 4 and Comparative Example 1, the voltage value was measured by energizing with an average current density of 10 kA/cm 2 , and the time when the voltage value became unmeasurable is shown in Table 2 as the breaking time.

Figure 0006713106
Figure 0006713106

（溶融性能試験）
各はんだ合金の溶融性能を測定した。
各はんだ合金の固相線温度及び液相線温度を示差走査熱量測定 (Differential scanning calorimetry；ＤＳＣ法)で昇温速度１０Ｋ／ｍｉｎにて測定した。
結果を表１に示す。(Melting performance test)
The melting performance of each solder alloy was measured.
The solidus temperature and the liquidus temperature of each solder alloy were measured by a differential scanning calorimetry (DSC method) at a heating rate of 10 K/min.
The results are shown in Table 1.

表１に示すように、実施例はいずれも破断時間が１５０時間以上であり、エレクトロマイグレーションの発生が抑制されていたことが明らかである。
また、実施例は固相線温度が２３０℃以上であり且つ液相線温度が２４０℃であった。すなわち、実施例では溶融性能が適切な範囲に調整されていた。As shown in Table 1, in each of the examples, the breaking time was 150 hours or more, and it is clear that the occurrence of electromigration was suppressed.
In the examples, the solidus temperature was 230°C or higher and the liquidus temperature was 240°C. That is, in the example, the melting performance was adjusted to an appropriate range.

さらに、表２に示すように、比較例１では、平均電流密度１０ｋＡ／ｃｍ２においても破断時間が短く、すなわち、エレクトロマイグレーションが生じていた。一方、実施例１及び４では、平均電流密度１０ｋＡ／ｃｍ２、及びより高い平均電流密度である５０ｋＡ／ｃｍ２、１００ｋＡ／ｃｍ２、２００ｋＡ／ｃｍ２においても、比較例１に比べて破断時間が長く、すなわち、エレクトロマイグレーションの発生がより抑制されていた。
以上より、各実施例では、幅広い電流密度の範囲において確実にエレクトロマイグレーションの発生が抑制されていたことが明らかである。


Furthermore, as shown in Table 2, in Comparative Example 1, the breaking time was short even at the average current density of 10 kA/cm 2 , that is, electromigration occurred. On the other hand, in Examples 1 and 4, the average current density of 10 kA / cm 2, and more a higher average current density 50kA / cm 2, 100kA / cm 2, even at 200 kA / cm 2, rupture time compared with Comparative Example 1 Was long, that is, the occurrence of electromigration was further suppressed.
From the above, it is clear that in each of the examples, the occurrence of electromigration was reliably suppressed in a wide current density range.


Claims (5)

Ｓｂ：３．０質量％超１０質量％以下、
Ａｇ：０．１質量％以上４．５質量％以下、
Ｃｕ：０質量％以上１．２質量％以下、
Ｎｉ：０質量％以上０．１質量％以下、
Ｃｏ：０質量％以上０．１質量％以下、
Ｇｅ：０．００１質量％以上０．１質量％以下、並びに、
残部：Ｓｎ及び不可避的不純物、
からなり、
前記Ｎｉ、Ｃｏ及びＧｅを合計で０質量％超０．１質量％以下含む鉛フリーはんだ合金。 Sb: more than 3.0% by mass and 10% by mass or less,
Ag: 0.1% by mass or more and 4.5% by mass or less,
Cu: 0 mass% or more and 1.2 mass% or less,
Ni: 0 mass% or more and 0.1 mass% or less,
Co: 0 mass% or more and 0.1 mass% or less,
Ge: 0.001 mass% or more and 0.1 mass% or less, and
Remainder: Sn and inevitable impurities,
Consists of
A lead-free solder alloy containing the total of Ni, Co and Ge in an amount of more than 0 mass% and 0.1 mass% or less. 前記Ａｇを０．１質量％以上４．０質量％以下含む請求項１に記載の鉛フリーはんだ合金。 The lead-free solder alloy according to claim 1, wherein the Ag content is 0.1% by mass or more and 4.0% by mass or less. 前記Ｃｕを０．１質量％以上１．０質量％以下含む請求項１又は２に記載の鉛フリーはんだ合金。 The lead-free solder alloy according to claim 1 or 2, wherein the Cu content is 0.1% by mass or more and 1.0% by mass or less. 請求項１乃至３のいずれか一項に記載の鉛フリーはんだ合金と、フラックスとを含むはんだ材料。 A solder material containing the lead-free solder alloy according to any one of claims 1 to 3 and a flux. 電極を有する基板と半導体素子とがはんだ接合部を介して接合された接合構造体であって、前記はんだ接合部は、請求項１乃至４のいずれか一項に記載の鉛フリーはんだ合金からなる接合構造体。 A joint structure in which a substrate having electrodes and a semiconductor element are joined via a solder joint, wherein the solder joint comprises the lead-free solder alloy according to any one of claims 1 to 4. Junction structure.
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